JPH02179637A - Silver halide color photographic sensitive material having superior color reproducibility - Google Patents

Abstract

PURPOSE:To retard generation of color fog of a dyestuff picture image and to improve preservability of picture images by incorporating a specified Cyan coupler and a specified compd. into a red-sensitive emulsion layer. CONSTITUTION:A Cyan coupler expressed by the formula I and a compd. expressed by the formula III are contained in a red-sensitive silver halide emulsion layer of the sensitive material. In the formula I, each R and Y is an H atom or a substituent; X is an H or an eliminable group; Z is a group of nonmetal atoms necessary for forming an N-contg. 6-membered heterocyclic group; Ar is arylene or cycloalkylene; RA is an alkyl or alkoxy group; M is H or an alkali metal atom, etc. Compds. expressed by the formula II may be used as the coupler expressed by the formula I. A compd. wherein Ar-RA is a group expressed by the formula IV and M is H, is used as the compd. expressed by the formula III.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, a silver halide color photograph that forms a dye image with little color cast and excellent image storage stability. Regarding photosensitive materials.

[Background of the invention]

After the silver halide photographic material is exposed to light, it is subjected to color development processing, whereby the oxidized aromatic primary amine color developing agent and the dye-forming coupler react to generate dyes and form a color image. Ru.

Generally, this photographic method uses a subtractive color reproduction method to form yellow, magenta and cyan color images.

Phenols or naphthols have been widely used as cyan image forming couplers.

However, cyan images obtained from conventionally used phenols and naphthols have serious problems in color reproduction. The reason is that the absorption is not sharp on the short wavelength side, and the edge region also has unnecessary absorption, that is, asymmetric absorption. As a result, in the case of negatives, it is necessary to correct the asymmetric absorption by masking or the like, and in the case of paper, there is no means for correction, and the current situation is that the color reproducibility is considerably deteriorated.

In addition, dye images obtained from conventionally used phenols and naphthols have some problems in their storage stability.For example, U.S. Pat.
The dye images obtained with the 2-acylaminophenolic cyan couplers described in U.S. Pat. No. 67.531 and U.S. Pat. The dye images obtained from the 2,5-diacylaminophenol cyan coupler described in No. 772,162 generally have poor light fastness, and the dye images obtained from the 1-hydroxy-2-natutamido cyan coupler generally have poor light fastness. Poor light and heat fastness.

Also, U.S. Patent No. 4,122,369 and Japanese Unexamined Patent Publication No. 5
2,5-diacylaminophenol cyan couplers described in specifications such as No. 7-155538 and JP-A-57-157246, and U.S. Patent No. 3,880,661.
The 2,5-diacylaminophenol cyan coupler that has a hydroxyl group in the ballast part described in the specification of the patent is also required in terms of fastness to light and heat and generation of yellow stain in order to preserve the dye image for a long time. However, a fully satisfactory level has not yet been achieved.

In order to solve this problem, Japanese Patent Application Nos. 62-203450, 32-203451, 63-7204, 63
-32094, 63-36086, 63-37
No. 998, No. 63-237681, etc., propose various pyrazolopyrimidone and pyrazoloquinazolone type cyan couplers.

It is true that the cyan images obtained from these cyan couplers have extremely excellent color reproducibility, and it is recognized that the thermal stability of the cyan images is also extremely excellent. It was found that it has the disadvantage of being larger than the .

When a multilayer color photographic material containing a color-forming coupler in a silver halide photographic emulsion is developed using a color developing agent such as rose phenylene diamine, an inconvenient "color cast" phenomenon occurs due to fogging of the emulsion, etc. is known.

In recent years, in the field of manufacturing technology for color photographic materials, in order to obtain even higher quality color photographs, color photographic materials have been developed that more efficiently prevent color cast without reducing photographic sensitivity. Great efforts are being made to do so.

[Object of the Invention] An object of the present invention is to provide a silver halide color photographic light-sensitive material that forms a dye image with little color cast and excellent image storage stability.

[Structure of the Invention] The object of the present invention is to provide a halogenated support having photographic constituent layers including a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer on a support. The silver photographic material is characterized in that the red-sensitive silver halide emulsion layer contains a cyan coupler represented by the following general formula [I], and further contains a compound represented by the following general formula Cs]. This can be achieved using a silver halide color photographic light-sensitive material.

General formula [I] May be condensed with a benzene ring other than the razole ring.] General formula [s3 Ar RA In the formula, Ar represents an arylene group or a cycloalkylene group, and RA represents an alkyl group, an alkoxy group, or a carboxyl group. group or its salt, sulfo group or its salt, hydroxyl group, amine group, acyl [wherein R and Y represent a hydrogen atom or a substituent, and represents a substituent,
Z represents a non-metallic atomic group necessary to form a nitrogen-containing 6-membered ring by condensation with the pyrazole ring together with -N-; 1-5 the 6-membered ring may have a substituent; , the piR' and R
r r each represents a hydrogen atom, an alkyl group, or an aryl group; 0M represents a hydrogen atom, an alkali metal atom, or an ammonium group.] [Specific Structure of the Invention] The present invention will be described in more detail below.

The cyan coupler of the present invention is fused with a pyrazole ring,
It has a structure forming a hetero6R ring, and the substituent represented by R is not particularly limited, but typically includes alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, and cycloalkyl. This group includes a halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, sulfonyloxy, aryloxy, heterocycleoxy, siloxy ,
Acyloxy, carbamoyloxy, amine, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, thioureido, carboxyl, hydroxy, mercapto, nitro, sulfone Also included are polygroups such as acids, spiro compound residues, bridged hydrocarbon compound residues, and the like.

The alkyl group represented by R preferably has 1 to 32 carbon atoms, and may be linear or branched.

The aryl group represented by R is preferably a phenyl group.

Examples of the acylamino group represented by R include an alkylcarbonylamino group and an arylcarbonylamino group.

Examples of the sulfonamide group represented by R include an alkylsulfonylamino group and an arylsulfonylamino group.

Examples of the alkyl component and aryl component in the alkylthio group and arylthio group represented by R include the alkyl group and aryl group represented by R above.

The alkenyl group represented by R preferably has 2 to 32 carbon atoms, and the cycloalkyl group preferably has 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms, and the alkenyl group may be linear or branched.

The cycloalkenyl group represented by R has 3 to 3 carbon atoms.
12, especially those of 5 to 7 are preferred.

Sulfonyl groups represented by R include alkylsulfonyl groups, arylsulfonyl groups, etc.; sulfinyl groups include alkylsulfinyl groups, arylsulfinyl groups, etc.; phosphonyl groups include alkylphosphonyl groups, alkoxyphosphonyl groups, and aryloxyphosphonyl groups. , arylphosphonyl group, etc. Niacyl groups include alkylcarbonyl groups, arylcarbonyl groups, etc.; carbamoyl groups include alkylcarbamoyl groups, arylcarbamoyl groups, etc.; sulfamoyl groups include alkylsulfamoyl groups,
Arylsulfamoyl group ring; As an acyloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group ring; As a carbamoyloxy group, an alkylcarbamoyloxy group, an arylcarbamoyloxy group, etc.; As an ureido group, an alkylureido group, an arylureido group, etc. : As the sulfamoylamino group, an alkylsulfamoylamino group, an arylsulfamoylamino group, etc.; As a heterocyclic group, a 5- to 7-membered one is preferable, and specifically, a 2-furyl group, a 2-thienyl group , 2-pyrimidinyl group, 2-benzothiazolyl group, 1-pyrrolyl group, 1-tetrazolyl group ring: The heterocyclic oxy group preferably has a 5- to 7-membered heterocycle, for example, 3,4,5.6- Tetrahydropyranyl-2-oxy group, 1-phenyltetrazole-5-
Oxy group ring: As the heterocyclic thio group, a 5- to 7-membered heterocyclic thio group is preferable, such as 2-pyridylthio group, 2-benzothiazolylthio group, 2,4-diphenoxy-1,3,5-1 lyazole -6-1000 group, etc.; Siloxy group includes trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc.; imide group includes succinimide group, 3-heptadecylsuccinimide group, phthalimide group, glutarimide group etc.; as a spiro compound residue, spiro[3,3]hebutane-
1-yl, etc.; As a bridged hydrocarbon compound residue, bicyclo[2°2.1
] heptan-1-yl, tricyclo[3゜3.1.13
-7] Decane-1-yl, 7,7-dimethyl-bicyclo[2,2,N-heptane-1-yl and the like.

The above group may further have a substituent such as a long-chain hydrocarbon group or a diffusion-resistant group such as a polymer residue. For example, halogen atoms (chlorine atom, bromine atom, fluorine atom, etc.) and alkoxy, aryloxy, heterocyclicoxy, acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio , arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocycle bonded by N atom, alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl, (R' is the same as the above R Z′ has the same meaning as Z, and Ra and Rb represent a hydrogen atom, an aryl group, an alkyl group, or a heterocyclic group.
Preferably it is a halogen atom. Among these, particularly preferred ones represented by X are hydrogen atoms and chlorine atoms.

A preferred specific example of the compound represented by the general formula [I] is represented by the following general formula [n].

General formula [II] Y# [wherein Z'' is fused to the pyrazole ring, and contains one -N- and at least one carbonyl group or at least one sulfonyl group and contains a nitrogen-containing Represents a group of nonmetallic atoms necessary to form a 6-membered hetero ring, and the 6@ring may have a substituent and may be condensed with a benzene ring in addition to the pyrazole ring, R'' and Y'' represents a hydrogen atom or a substituent, and X'' represents a hydrogen atom or a substituent that is eliminated by reaction with the oxidized product of the coloring developer.] The compound represented by the general formula [II will be explained in more detail. .

In formula CI], the nitrogen-containing 6-membered hetero ring formed by Z is preferably a 6π electron system or an 8π electron system,
It contains 1 to 4 nitrogen atoms including at least one -N-, and the at least one carbonyl group contained in the 6R ring represents a group such as >C=O or >C=S, or , the at least one sulfonyl group contained in the 6-membered ring is -
Represents an S- group.

In the general formula [II, Y represents a hydrogen atom or a substituent, and the preferable disubstituted group represented by Y is, for example, one which is eliminated from the compound of the present invention after the compound reacts with the oxidized developing agent. However, for example, the substituent represented by Y may be a group that can be separated under alkaline conditions as described in JP-A No. 61-228444, etc., or a group that can be separated under alkaline conditions as described in JP-A No. 56-133734, etc. As described,
Examples include substituents that are coupled off by reaction with the oxidized developing agent, and preferably Y is a hydrogen atom.

Among the compounds represented by the general formula [11], preferred specific examples include the following general formulas [II-al, [■-b], [I
Examples include compounds represented by [I-c] and [I[-d].

The following margins are general formula [II-al general formula [I[-bl general formula [II-c] R1 general formula [n-d] [wherein R1-R2 and R1 are synonymous with R in general formula [II] , X has the same meaning as X in the general formula [II, and Y has the same meaning as Y in the general formula [II]. In the general formula [1l-bl, n represents an integer of 0 to 4,
When n is an integer from 2 to 4, multiple R2s may be the same or different.] General Number Counter II al, R2 and R1 in [I[-c and [II-d] are represented by the general formula [
1], except that R2 is not a hydroxy group.

Preferred examples of R2 and R1 include polygroups such as alkyl groups, aryl groups, carboxyl groups, oxycarbonyl groups, cyano groups, alkoxy groups, aryloxy groups, amino groups, amide groups, and sulfonamide groups, and hydrogen atoms; These include halogen atoms.

Next, typical compound examples of the present invention are shown below, but the present invention is not limited thereto.

Below is a margin X ■ H Next, a typical synthesis example of the compound of the present invention is shown below. ) of 5-amino-3-phenylpyrazole and 15.9t (0.1 mol) of 2-ethoxycarbonylacetimidic acid ethyl ester at 200%
After heating and refluxing the 0 reaction solution in dehydrated ethanol for 2 hours, the P solution was cooled and the formed precipitate was collected, washed with cold ethanol, and then mixed with dimethylformamide and water. Recrystallization from a solvent gave 17.8ir (0,079 mol) of white needle-like crystals of compound a.

(Compound a) Melting point: 300°C or higher The structure of the compound was confirmed by NMR spectrum and mass spectrum.

[Synthesis of compound (A-13) from compound viewpoint] Compound a1
7.0 g (0,075 mol) of ethyl acetate solution 600
100 ml of an ethyl acetate solution containing 31.2 g (0,075 mol) of Compound b was added to m1, and 7.8 g of triethylamine was added thereto. The mixture was stirred at room temperature for 2 hours, and the precipitated crystals were collected. This was washed with water and further recrystallized with acetonitrile to give white needle-like crystals of compound (A-13) 23. Or (0,038 mol) was obtained.

The compound (
The structure of A-13> was confirmed.

Synthesis Example 2 [Synthesis of Compound (B-1)] [Synthesis of Compound] The above compound c 16.2g (0.1 mol) and the above compound d 34.8r (0.1 mol) were mixed into 40+III f
) Meta/-R6: After dissolving, the reaction solution was stirred at room temperature for 2 hours, then 9.8 g of sodium carbonate was added, and the reaction solution was stirred at 50°C for 2 hours.
ml of water, neutralized using hydrochloric acid, and the resulting solid precipitated was recrystallized from a mixed solvent of toluene and acetonitrile to obtain the above compound in the form of white crystals.
．． 8° (0.03 mol) was obtained.

[Synthesis of compound (B-1) from the viewpoint of compounds] Next, this compound e 10. Og < 0.023 mol) to 10
The mixture was dissolved in 0 ml of acetic acid, and 35 ml of 35% hydrogen peroxide solution was slowly added dropwise to the resulting solution, followed by stirring at 50° C. for 3 hours. Add 300ml of water to this solution and
Neutralize with an aqueous sodium hydroxide solution at a temperature below ℃, extract the resulting solution with ethyl acetate, distill off the ethyl acetate from the extract, and recrystallize the formed precipitate using acetonitrile. Then, 8.5 g (<0.018 mol) of compound (B-1) crystallized as a white powder was obtained.

The compound (
The structure of B-1) was confirmed.

Synthesis Example 3 [Synthesis of compound (C-5)] [Synthesis of compound] Ethyl-3,5-diaminopyrazole-4-carboxylic acid 17.0 g (0.1 mol), p-dodecaoxyphenylsulfonyl chloride 36.1 g (0.1 mol) and 15.2 g (0.15 mol) of triethylamine in 50
The mixture was added to 0 ml of ethyl acetate and heated under reflux for 1 hour.

After cooling, the precipitated crystals were taken out, washed with water, and heated to 29.6° (0
, 06 mol) was obtained.

[Synthesis from compound view to compound view 29.1t (0,059 mol) compound view and il
l, eg (0,089 mol) of α-chloroacetoacetic acid ethyl ester was heated in 600 ml of toluene for 6 hours.
The mixture was refluxed to perform a dehydration reaction.

The reaction solution was concentrated under reduced pressure to obtain crude crystals, which were recrystallized from ethanol to yield 16.1 g of white needle-like crystals representing the compound.
<0.027 mol) was obtained.

The structure of the compound was confirmed by NMR spectrum and mass spectrum.

[Synthesis of compound (C-5) from compound perspective] Compound 115
．． 4t (0,026 mol) of acetic acid, sulfuric acid, compound (C
-5) Dissolved in 130 ml of water mixed solvent (100:25:5) and heated under reflux for 1 hour. After adjusting the concentration to ρ■5 with an aqueous sodium hydroxide solution, extraction was performed with ethyl acetate, the solvent was dried over Rh magnesium, and the mixture was distilled off. The residue was recrystallized from acetonitrile to obtain white needle-like crystals of compound (C-5) 7.3.
(0,014 mol) was obtained.

The compound (
The structure of C-5) was confirmed.

Synthesis IM4 [Synthesis of compound (D-5)] Compound (D-5
) [Synthesis of Compound L] 45ir (0.1 mol) of Compound L (used in Synthesis Example 3) and 22 g (0.1 mol) of ω-acetophenonesulfonyl chloride were added to 1 J of chloroform, and further 12 g ( 0.12 mol) of triethylamine was added, heated and refluxed for 5 hours, cooled, and the reaction solution was diluted with dilute hydrochloric acid.
After washing twice, chloroform was distilled off under reduced pressure, and recrystallized twice from methanol to obtain 30 g of white powder crystals, which is the compound
(0,045 mol) was obtained.

The structure of the compound was confirmed by NMR spectrum and mass spectrum.

[Synthesis on a compound from a compound] 20g <0.03 mol) of a compound 140-16
After heating at 0°C for 1 hour and cooling, the precipitated crystals were recrystallized with ethanol to obtain gray-white powder crystals 9, a, which are on the compound.
, (0,015 mol) was obtained.

The structure of the compound was confirmed by NMR spectrum and mass spectrum.

[Synthesis of compound (D-5) from above the compound] Compound (D-5) was synthesized from above 6.3 g (0.01 mol) of the compound in exactly the same manner as the method for obtaining the compound (C-5> from above the compound in Synthesis Example 3). 2.9g of white powder crystals (0,0
05 mol) was obtained.

The compound (
The structure of D-5) was confirmed.

The cyan couplers of the present invention are usually used per mole of silver halide to lX1 G'' mole, preferably lX10-2
It can be used in the range of -8 x 10-' moles.

The coupler of the present invention can also be used in combination with a pond type cyan coupler.

In order to incorporate the cyan coupler according to the present invention into the color photosensitive material of the present invention, known techniques used for ordinary cyan couplers can be applied.

It is preferable to dissolve the coupler in a high-boiling point solvent and, if necessary, in combination with a low-boiling point solvent, disperse the coupler in the form of fine particles, and add it to the silver halide emulsion according to the present invention.

At this time, if necessary, a hydroquinone derivative, an ultraviolet absorber, an anti-fading agent, etc. may be used in combination.

Next, the compound represented by the general formula [S] will be explained.

In the silver halide photographic material of the present invention, the red-sensitive silver halide emulsion layer contains a compound represented by the general formula [S].

In the general formula [S], examples of the arylene group represented by Ar include a phenylene group and a naphthylene group, and examples of the cycloalkylene group include a cyclohexylene group.

Examples of the alkyl group represented by RA include methyl group,
Examples of the alkoxy group include a methoxy group and a propoxy group; examples of the acylamino group include an acetylamino group, a hexanoylamino group, a benzoylamino group, and a sodium atom and a potassium atom.

Specific examples of the compound represented by the general formula [S] are shown below, but the present invention is not limited thereto.

Below, examples of blank spaces include N-methylcarbamoyl group, N-7enylcarbamoyl group, etc., and examples of NH30aR'' include methylsulfonylamino group, benzenesulfonamide group, etc., N-methylureido group, N-ethylureido group, etc. ,N,N
-dimethylureido group, N,N-diethylureido group,
Examples include N-phenylureido group. The multiple groups represented by RA include those having further substituents.

Examples of the alkali metal atom represented by M include r R
A Compounds represented by the general formula [3] are disclosed in, for example, U.S. Pat.
It can be synthesized according to the method described in, for example, No.-138732.

The compound represented by the general formula [3] according to the present invention (hereinafter,
In order to incorporate the compound (referred to as "compound [S]") into the silver halide emulsion layer according to the present invention, an organic solvent that is arbitrarily miscible with water (for example, methanol, ethanol, etc.) should be used instead of water.
The compound [S] may be added after being dissolved in the compound [S], and may be used alone, or a compound represented by the general formula [S],
Alternatively, it may be used in combination with other stabilizers or fog suppressants other than the compound represented by the general formula [S].

The timing of adding the compound [S] is before the formation of silver halide grains, during the formation of silver halide grains, from after the completion of silver halide grain formation to before the start of chemical ripening, during chemical ripening, at the end of chemical ripening, It may be added at any time from the end of chemical ripening to the time of coating, preferably during chemical ripening, at the end of chemical ripening, or from the end of chemical ripening to the time of coating. The entire amount may be added at one time, or may be added in multiple portions.

It can be added directly to the silver halide emulsion or silver halide emulsion coating solution, or it can be added to the coating solution for the adjacent non-photosensitive hydrophilic colloid layer, and it can be added to the main layer by diffusion during multilayer coating. It may be contained in the silver halide emulsion layer according to the invention.

There is no particular restriction on the amount added, but it is usually 1 x 10-' mole to I x 10-' mole per mole of silver halide.
'mol, preferably 1 x 10-5 mol to I x 10
−' molar range.

Examples of the silver halide used in the silver halide emulsion layer of the sensitive material of the present invention include silver chloride, silver bromide, silver iodide,
Any of those used in conventional silver halide photographic emulsions, such as silver chlorobromide, silver iodobromide, and silver chloroiodobromide, are included.

These silver halide grains may be coarse or fine, and the grain size distribution may be narrow or wide.

Further, the crystals of these silver halide grains may be normal crystals or twin crystals, and any ratio of the (100) plane to the [1113 plane can be used. Furthermore, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may have a layered structure with different inside and outside parts. It may be of a type that forms a latent image mainly on the surface or of a type that forms a latent image inside the particle.

These silver halide grains can be prepared by known methods commonly used in the art.

It is preferable that soluble salts be removed from the silver halide emulsions used in the light-sensitive materials of the present invention, but those in which soluble salts have not been removed can also be used. It is also possible to use a mixture of two or more silver halide emulsions prepared separately.

The silver halide emulsion used in the present invention includes:
Any silver halide emulsion may be used, such as silver chloride emulsion, silver chlorobromide emulsion, silver chloroiodromide emulsion, etc., but there are no particular limitations.
Silver halide emulsions having high chloride silver halide grains are preferred.

The above-mentioned high chloride silver halide grains refer to those having a silver chloride content of 90 mol% or more.In the high chloride silver halide grains, the silver bromide content is 10 mol% or less,
The silver iodide content is preferably 0.5 mol% or less, and more preferably silver chlorobromide has a silver bromide content of 0.1 to 2 mol%.

High chloride silver halide grains do not have to be used alone, but can also be used in combination with other silver halide grains having different compositions.

For example, it may be mixed with silver halide grains having a silver chloride content of 10 mol % or less.

In addition, in a silver halide emulsion layer containing high chloride silver halide grains, the proportion of high chloride silver halide grains in the total silver halide grains contained in the emulsion layer is 60% by weight or more. The amount is preferably 80% by weight or more, and more preferably 80% by weight or more.

The composition of high chloride silver halide grains may be uniform from the inside to the outside of the grain, or the composition inside and outside the grain may be different, or the composition inside and outside the grain may be different. In this case, the composition may change continuously or discontinuously.

There is no particular restriction on the grain size of the high chloride silver halide grains, but in consideration of other photographic performance such as rapid processing and sensitivity, it is preferably 0.2 to 1.6 μm, more preferably 0.2 μm to 1.6 μm, more preferably 0.2 to 1.6 μm.
It is in the range of 25 to 1.2 μm. In addition, the above particle diameter is
It can be measured by various methods commonly used in the art.

Typical methods include Loveland's "particle size analysis method,"
(A, S, T, M, Symposium on Light Microscopy, 1955, pp. 94-122) or “
"A Theory of the Photographic Process" (Chapter 2, by Mies and James, 3rd edition, published by Macmillan, 1966)
It is described in.

This particle size can be measured using either the projected area of the particle or an approximation to its diameter.If the particles are of substantially uniform shape, the particle size distribution will measure this fairly accurately as the diameter is the projected area. can be expressed.

The grain size distribution of the high chloride silver halide grains may be polydisperse or monodisperse.

Preferably, the silver halide grains are monodisperse silver halide grains having a coefficient of variation of 0.22 or less, more preferably 0.15 or less in the grain size distribution.

The silver halide grains used in the emulsion of the present invention can be prepared by acidic method.
It may be obtained by either the neutral method or the ammonia method. The particles may be grown all at once, or may be grown after seed particles are produced.

The method of creating and growing the seed particles may be the same or different.

In addition, the method for reacting the soluble silver salt with the soluble halogen salt may be any method such as a forward mixing method, a back mixing method, a simultaneous mixing method, or a combination thereof, but it is preferable to use a method obtained by a simultaneous mixing method. I) Afll- described in Japanese Patent Application Laid-Open No. 54-48521 etc. as a form of the law
It is also possible to use the Chondrold-double jet method.

Furthermore, if necessary, a silver halide solvent such as a thioether may be used, and a compound such as a mercagut group-containing compound, a nitrogen-containing heterocyclic compound, or a sensitizing dye may be used during the formation of silver halide grains or It may be added and used after the completion of formation.

The silver halide grains used in the present invention may have any shape. One preferred example is +1oot
It is a cube with planes as crystal surfaces.

Further, particles having shapes such as an octahedron, a tetradecahedron, a dodecahedron, etc. can also be used. Furthermore, particles having twin planes may be used.

The silver halide grains used in the present invention may be of a single shape or may be a mixture of grains of various shapes.

The silver halide grains used in the present invention may contain cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts, rhodium salts or complex salts,
Metal ions can be added to the inside of the particles and/or on the surface of the particles by using iron salts or complex salts, and reduction-sensitized nuclei can be formed inside the particles and/or on the surface of the particles by placing them in an appropriate reducing atmosphere. can be granted.

In the emulsion containing silver halide grains used in the present invention (hereinafter referred to as "emulsion of the present invention"), unnecessary soluble salts may be removed after the growth of the silver halide grains is completed;
Alternatively, in the case of removing the salts, which may remain contained, the method described in Research Disclosure No. 17843 can be used.

The silver halide grains used in the emulsion used in the present invention are:
Preferably, the particles are particles in which the latent image is mainly formed on the surface, but particles in which the latent image is formed inside the particles may also be used.

In the present invention, a chalcogen sensitizer can be used. Chalcogen sensitizer is a general term for sulfur sensitizers, selenium sensitizers, and tellurium sensitizers, and sulfur sensitizers and selenium sensitizers are preferable. Examples of sulfur sensitizers include thiosulfates and aliphatic sensitizers. ruthiocarbazide, thiourea, allyl isothiocyanate, cystine, p-toluenethiosulfonate,
Examples include rhodanine. Others, U.S. Patent 1.574
．． No. 944, No. 2,410,689, No. 2,278,
No. 947, No. 2.728,668, No. 3,501,3
No. 13, No. 3.656.955, West German Application Publication (OL
S) No. 1,422,869, JP-A-56-24
Sulfur sensitizers described in No. 937, No. 55-45016, etc. can also be used. The amount of sulfur sensitizer added varies over a considerable range depending on various conditions such as pH, temperature, and the size of silver halide grains, but as a guide, it is 10-7 mol to 10-7 mol per mol of silver halide.
About 1 mol is preferable.

The emulsion of the present invention can be produced by a reduction sensitization method using a reducing substance, a noble metal sensitization method using a noble metal compound, or the like.

In the photographic constituent layer containing the cyan coupler according to the present invention,
By including the high chloride silver halide emulsion, faithful color reproducibility and sufficient maximum density can be obtained.

The silver halide emulsion used in the present invention can be optically sensitized to a desired wavelength range using a dye known as an enhancing dye in the photographic industry.

As the binder (or protective colloid) used in the silver halide photographic material of the present invention, it is advantageous to use gelatin, but gelatin derivatives, graft polymers of gelatin and polymers, proteins, and sugar derivatives may also be used. Hydrophilic colloids such as cellulose derivatives, synthetic hydrophilic polymeric substances such as monopolymers or copolymers can also be used.

The silver halide photographic light-sensitive material of the present invention having the above structure can be, for example, color negative and positive films, color photographic paper, etc., but in particular color photographic paper used for direct viewing can be used. In such cases, the effects of the method of the present invention are effectively exhibited.

When the silver halide color photographic light-sensitive material of the present invention is used as a full-color light-sensitive material, a magenta coupler and a yellow coupler are used in addition to the cyan coupler of the present invention. There are no particular restrictions on the magenta coupler and the yellow coupler, and known ones can be used.

As the magenta coupler, 5-pyrazolone type, pyrazolobenzimidazole type, pyrazoloazole type, open chain acylacetonitrile type Kaglar etc.
-Pyrazolone and pyrazolotriazole magenta couplers are preferred.

As the yellow coupler, for example, acylacetanilide couplers can be used, including benzacetanilide and pivaloylacetanilide compounds.

The silver halide photographic material of the present invention further includes a hardening agent, an anti-irradiation agent, an anti-color clouding agent, an image stabilizer, a plasticizer, a latex, a surfactant, a matting agent, a lubricant, and an antistatic agent. Additives such as the following can be used as necessary.

An image can be formed on the silver halide photographic material of the present invention by subjecting it to color development treatment known in the art.

The pH value of the color development temperature is usually above 7, most commonly about 10 to 13.

The color development temperature is usually 15°C or higher, numerically -20°C.
It is in the range of °C to 50 °C. 30°C for quick development
The color development time of the present invention, which aims at rapid processing, is generally 20 seconds to 60 seconds, whereas conventional processing takes 3 to 4 minutes. is preferable, and more preferably in the range of 30 seconds to 50 seconds.

The silver halide photographic light-sensitive material of the present invention can be rapidly developed without decreasing the maximum density of the characteristic curve even when using a color developing solution containing 2 ml or less of benzyl alcohol per 1β used for rapid development. .

After color development, bleaching and fixing are performed.

Bleaching treatment may be performed simultaneously with fixing treatment.

After the fixing process, a washing process is usually performed.

Further, as an alternative to the water washing treatment, a stabilization treatment may be performed, or both may be used in combination.

〔Example〕

Although specific embodiments of the present invention are described above, embodiment B of the present invention is not limited to these.

Example 1 On a paper support laminated with polyethylene, the following layers were sequentially coated from the support side to obtain a silver halide color photographic material comparison sample NQ1t! -Created.

Layer 1...1, 2g/- gelatin, 0.32
g/rf silver equivalent, hereinafter the same) blue-sensitive silver halide emulsion (silver chloride content 97 mol%, sodium thiosulfate 2R/silver halide 1 mol as a chemical sensitizer and 5D-10 as a spectral sensitizer) , 9 mmol/1 mole of silver halide), 0.50 g/r
0,80 g/r dissolved in +f dioctyl phthalate
A layer containing yellow coupler (Y-A) of rr.

Layer 2...0.7g/lrr gelatin, 30■
/d irradiation dye (AI-1).

Intermediate layer consisting of (AI-2) of 20 μ/d.

Layer 3---1.25 g/rd gelatin,
Green-sensitive silver halide emulsion of 0.22 g/rrl (silver chloride content 100 mol%, 2 q of sodium thiosulfate/1 mol of silver halide as chemical sensitizer and 0.7 mmol of 5D-2 as spectral sensitizer) / Contains 1 mole of silver halide.)
, 0.62g/rr dissolved in 0.30g/rrr of dioctyl phthalate. magenta coupler (M-A)
A layer containing.

Layer 4: Intermediate layer consisting of 1.2 g/d gelatin.

Layer 5...1.40g/nf gelatin, 0.2
Red-sensitive silver halide emulsion of 0g/g (silver chloride content 100 mol%, sodium thiosulfate as chemical sensitizer/f!1 mol of halide and 5 as spectral sensitizer)
D-3 Contains 0.2 mmol/1 mole of silver halide. )
, 0.45 g/rd of cyan coupler (CC-1) dissolved in 0.20 g/r+f of tri-n-octyl phosphate.

Layer 6: Layer containing 0.5 g/rrr of gelatin.

In addition, as a hardening agent, 2,4-dichloro6-hydroxy-s-triazine sodium was added in layers 2, 4 and 6.
Each was added in an amount of 0.017 g per 1 g of gelatin.

Next, when preparing the red-sensitive silver halide emulsion used in layer 5, after chemical aggravation, 1x1
Comparative sample 11112 was prepared in the same manner as comparative sample 111QI except that 0-'mol of comparative compound-8 was added.

Next, in place of comparative compound-8, compound S-6 of the present invention
Comparative sample NQ3 was prepared in the same manner as comparative sample 2 except that .

Furthermore, 0.45g of cyan coupler used in layer 5
/rd's (cc-1) instead of 0.63g/rrr
(0,0009 mol/ba) of coupler A-13 of the invention
Comparative sample NQ 4 was prepared in the same manner as comparative sample NQ 1 except that .

Below, the cyan couplers shown in Table 1 (0,0009 mol/
rrF) and comparative compound-8 or the compound represented by general formula [S] (1xlO-' mol/silver halide 1 mol) to prepare comparative sample NQ5 and present invention sample Nα1.
~1 (Y-A) (M-A) 1 was created.

(AI-1) H3 H3 (SD-2) (AI-2> (SD-3) gHs Comparative compound-8 H Obtained above photosensitive material Comparative samples NQ 1 to 5 and present invention samples NQ1 to 11 were each 2M Get ready.

The first set was subjected to wedge exposure using a sensitometer KS-7 model (manufactured by Konica Corporation), and then processed according to the following color development process. 65 type) to measure the fog density of the red-sensitive emulsion layer and evaluate the immediate color fog.

In addition, each of the above treated samples was heated at high temperature (60℃, 80%
The heat resistance and moisture resistance of each dye image were evaluated based on the density of the dye remaining after the dye was left in an atmosphere (RH) for 10 days, and the dye residual rate was expressed as a percentage of the initial density.

Furthermore, two of the two sets of the obtained photosensitive materials were added.
The assembly was left in a high temperature/high temperature (50°C, 80% RH) atmosphere for 3 days, and then the same wedge exposure and color development process as described above was performed, and the resulting dye image was
The fog density of the red-sensitive emulsion layer was measured to evaluate the color fog over time.

Table 1 shows the evaluation results for heat resistance/humidity, immediate color cast, and color cast over time.

Processing process> Temperature color development 34.7°C 0.3"C Bleach fixing 34.7±0.5"C Stabilization 30-34°C Drying 60-80°C Color developing solution> Pure water triethanolamine N,N-diethylhydroxyamine Potassium chloride N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate Sodium tetrapolyphosphate Potassium carbonate Potassium [acid] Optical brightener (4,4 '-diaminostilbendisulfonic acid derivative) Time 0 hours 45 seconds 50 seconds 90 seconds 60 seconds g g 0g 0.2g Add pure water to make the total amount IJ, and adjust the pHIQ to 2.

Bleach-fix solution> Ethylenediaminetetraacetate ferric ammonium dihydrate sog ethylenediaminetetra#6 3g ammonium thiosulfate (70% solution) 100mj ammonium sulfite (40% solution) 27.5mf Potassium carbonate or glacial acid to pH 5.7 Adjust and add water to bring the total volume to 11.

Stabilizing liquid> 5-chloro-2-methyl-4-inthiazolin-3-one 1g 1-hydroxyethylidene-1゜1-diphosphonic acid 2g Add water to make 11, and adjust DH to 7 with Kfa or potassium hydroxide. Adjust to .0.

Table 1 Margin below From the results in Table 1, the following can be seen. When the comparative cyan coupler (CC-1) was used, the heat and humidity resistance of the resulting dye image was considerably poor, and even when the compound of the present invention [SF] was used in combination, no significant improvement in color cast was observed.

However, when the cyan coupler of the present invention is used, the heat and humidity resistance of the generated dye image is very good, and the color cast, which was a drawback, can be greatly reduced by using the compound [3] of the present invention. It was found that it could be improved.

[Effects of the Invention] The silver halide color photographic light-sensitive material of the present invention reduces color cast and realizes dye images with excellent storage stability.

Claims (1)

[Scope of Claims] A silver halide photographic light-sensitive material having photographic constituent layers including a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support. , the red-sensitive silver halide emulsion layer has the following general formula [
A silver halide color photographic light-sensitive material, characterized in that it contains a cyan coupler represented by the formula [I] and further contains a compound represented by the following general formula [S]. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R and Y represent hydrogen atoms or substituents,
X represents a hydrogen atom or a substituent that leaves by reaction with an oxidized product of a color developing agent, Z represents a ▲numerical formula, chemical formula, table, etc. ▼ and is condensed with the pyrazole ring to form a nitrogen-containing 6-membered hetero ring. It represents a group of nonmetallic atoms necessary for forming the 6-membered ring, which may have a substituent, and may be condensed with a benzene ring in addition to the pyrazole ring. ] General formula [S] ▲ Numerical formulas, chemical formulas, tables, etc. , hydroxyl group, amino group, acylamino group, ▲Mathematical formulas, chemical formulas, tables, etc. are available▼, -NHSO_2R' or ▲Mathematical formulas, chemical formulas, tables, etc. are available▼. R' and R'' each represent a hydrogen atom, an alkyl group, or an aryl group. M represents a hydrogen atom, an alkali metal atom, or an ammonium group.]